EP0958266B1 - Verfahren zur herstellung von halogenkohlenwasserstoffen - Google Patents

Verfahren zur herstellung von halogenkohlenwasserstoffen Download PDF

Info

Publication number
EP0958266B1
EP0958266B1 EP98902505A EP98902505A EP0958266B1 EP 0958266 B1 EP0958266 B1 EP 0958266B1 EP 98902505 A EP98902505 A EP 98902505A EP 98902505 A EP98902505 A EP 98902505A EP 0958266 B1 EP0958266 B1 EP 0958266B1
Authority
EP
European Patent Office
Prior art keywords
ccl
group
copper
integer
catalyst
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP98902505A
Other languages
English (en)
French (fr)
Other versions
EP0958266A1 (de
Inventor
Allen Capron Sievert
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
EIDP Inc
Original Assignee
EI Du Pont de Nemours and Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by EI Du Pont de Nemours and Co filed Critical EI Du Pont de Nemours and Co
Publication of EP0958266A1 publication Critical patent/EP0958266A1/de
Application granted granted Critical
Publication of EP0958266B1 publication Critical patent/EP0958266B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
    • C07C17/272—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by addition reactions
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C19/00—Acyclic saturated compounds containing halogen atoms
    • C07C19/08—Acyclic saturated compounds containing halogen atoms containing fluorine
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
    • C07C17/20—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms
    • C07C17/202—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms two or more compounds being involved in the reaction
    • C07C17/206—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms two or more compounds being involved in the reaction the other compound being HX
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/23—Preparation of halogenated hydrocarbons by dehalogenation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
    • C07C17/272—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by addition reactions
    • C07C17/275—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by addition reactions of hydrocarbons and halogenated hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
    • C07C17/272—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by addition reactions
    • C07C17/278—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by addition reactions of only halogenated hydrocarbons

Definitions

  • This invention relates to a process for the manufacture of halogenated alkanes using the catalytic reaction of haloalkanes with halogenated olefins.
  • haloalkanes e.g., AB, where A is a substituted carbon atom and B is a halogen other than fluorine
  • the products i.e., halogenated addition compounds
  • telomers e.g., A(CH 2 CHR) n B, where n is equal to 2 or more.
  • 2,073,533 discloses a process for the manufacture of CCl 3 CH 2 CCl 3 by reacting carbon tetrachloride with vinylidene chloride using copper catalysts in acetonitrile.
  • the selectivity for CCl 3 CH 2 CCl 3 with respect to converted vinylidene chloride was 87%. It has been shown in the art that the major by-product is the C 5 telomer, CCl 3 (CH 2 CCl 2 ) 2 Cl.
  • the catalyzed addition of haloalkanes to olefins is done in a homogeneous medium, separation of the catalyst from the product can present difficulties. This is especially so when it is desired to run the reaction in a continuous manner.
  • 3,651,019 discloses a process for the production of 1:1 adducts of carbon tetrachloride or chloroform with olefinically unsaturated compounds in the presence of iron or copper catalysts, which are at least partially in reduced valence states.
  • halogenated adducts are useful intermediates for the production of fluoroalkanes, particularly, hydrofluoroalkanes. These latter compounds are useful as refrigerants, fire extinguishants, heat transfer media, propellants, foaming agents, gaseous dielectrics, sterilant carriers, polymerization media, particulate removal fluids, carrier fluids, buffing abrasive agents, displacement drying agents and power cycle working fluids.
  • fluoroalkanes particularly, hydrofluoroalkanes.
  • a liquid phase process is provided in accordance with this invention for producing halogenated alkane adducts of the formula CAR 1 R 2 CBR 3 R 4 wherein R 1 , R 2 , R 3 , and R 4 are each independently selected from the group consisting of H, Br, Cl, F, C 1 -C 6 alkyl, CN, CO 2 CH 3 , CH 2 Cl, and aryl (e.g., phenyl), provided that when either R 3 or R 4 is selected from the group consisting of C 3 -C 6 alkyl, CN, CO 2 CH 3 , CH 2 Cl, and aryl, then R 1 , R 2 , and the other of R 3 and R 4 are H, and when R 3 and R 4 are selected from the group consisting of Cl, F, CH 3 and C 2 H 5 , then R 1 and R 2 are H, and when either R 1 or R 2 and either R 3 or R 4 are selected from the group consisting of Cl, F, CH 3 and C 2 H 5 , then the other
  • This invention further provides a process for producing hydrofluoroalkanes (e.g., CF 3 CH 2 CHF 2 ).
  • AB e.g., CCl 4
  • saturated, halogenated alkanes to alkenes to form adducts
  • a wide range of saturated, halogenated alkanes may be used in the process of the invention.
  • suitable saturated, halogenated alkanes are given by Walling and Huyser in Tables V, VI, VII, and VIII in Chapter 3 of Organic Reactions, Vol. 13 (1963).
  • Halogenated alkanes, AB that are particularly useful for the process of this invention include certain compounds where A is selected from the group consisting of CX 3 , CH 3-a X a , C n H (2n+1)-b X b and CH c X 2-c R where each X is Br, F, Cl or I and R is C n H (2n+1)-b X b (e.g., CF 3 and CCl 2 CF 3 ); and B is Br, Cl or I. Included are compounds where A is CX 3 and only one of X is I.
  • A is CH 3-a X a where X is B and where when X is Br or Cl, a is 2, and when X is I, a is an integer from 0 to 2. Also included are the compounds where A is C n H (2n+1)-b X b , where each X is independently selected from Cl and F, n is an integer from 1 to 6, b is an integer from 1 to 2n+1, and B is I. Also included are compounds where A is CH c X 2-c R wherein c is an integer from 0 to 1.
  • saturated, halogenated alkanes suitable for the process of this invention include CCl 4 , CBrCl 3 , CCl 2 FCCl 2 F, CCl 3 CClF 2 , CCl 3 CF 3 , CCl 3 CF 2 CCl 3 , CCl 3 CF 2 CF 3 , CCl 3 CH 2 CCl 3 , CCl 3 CH 2 CF 3 , CCl 3 CF 2 CClF 2 , CF 3 I, CF 3 CF 2 I, CF 3 CFICF 3 and CF 3 CF 2 CF 2 I.
  • alkenes may be used in the process of the invention.
  • suitable alkenes are given by Walling and Huyser in Tables V, VI, VII, and VIII in Chapter 3 of Organic Reactions, Vol. 13 (1963).
  • the addition of halogenated alkanes to alkenes to form the corresponding adducts is catalyzed by copper(I) compounds, that is, copper compounds in the +1 oxidation state.
  • Preferred copper compounds for the process of this invention include copper(I) chloride, copper(I) bromide, copper(I) iodide, copper(I) acetate, and copper(I) thiocyanate.
  • Especially preferred copper compounds for the process of this invention include copper(I) chloride and copper(I) bromide.
  • the catalysts are preferably anhydrous; and preferably, the addition of halogenated alkanes to alkenes is done under substantially anhydrous conditions in the substantial absence of oxygen.
  • the effect of the catalyst is to enhance the yield of the 1:1 addition product (i.e., the adduct) of the halogenated alkanes to the alkene relative to higher molecular weight telomers that are known in the art.
  • Suitable soluble salts for the process of this invention include substituted ammonium halides, pyridinium and substituted pyridinium halides, and quaternary salts of the type (MQ 4 )Y where M is an element of Group VA of the Periodic Table (i.e., N, P, As, Sb, or Bi), Q is independently selected from the group consisting of C 1 -C 18 acyclic or cyclic alkyl, benzyl (CH 2 C 6 H 5 ), phenyl (C 6 H 5 ), substituted benzyl, or substituted aryl, and Y is chloride, bromide or iodide. Mixtures of these soluble salts may also be used.
  • substituted ammonium halides include HY adducts of alkylamines (QNH 3 Y), aryl amines (ArNH 3 Y), dialkylamines (Q 2 NH 2 Y), and trialkylamines (Q 3 NHY) where Y and Q are as defined above.
  • Specific examples of these types of compounds include ethylamine hydrochloride, benzylamine hydrochloride, anilinium chloride, dimethylamine hydrochloride, piperidine hydrochloride, piperazine dihydrochloride, trimethylamine hydrochloride, triethylamine hydrobromide, and triethylamine hydrochloride.
  • pyridinium and substituted pyridinium halides include pyridinium chloride, N-methyl pyridinium bromide, and 1-tetradecyl-3-picolinium chloride.
  • quarternary ammonium halides include tetramethylammonium chloride, tetramethylammonium bromide, tetraethylammonium bromide, tetraethylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium chloride, tetra-n-hexylammonium bromide, benzyltrimethylammonium bromide, tricaprylylmethyl chloride, benzyltributylammonium bromide, dodecyltrimethylammonium bromide, tetra-n-amylammonium chloride, and decamethylenebis(trimethylammonium bromide).
  • quaternary salts of the type (MQ 4 )Y include tetraphenylphosphonium chloride, tetraphenylphosphonium bromide, n-hexadecyltributylphosphonium bromide, methyltriphenylphosphonium bromide, and tetraphenylarsonium chloride.
  • the copper catalyst for the process of the invention may also, if desired, be further promoted by certain heterocyclic non-ionic compounds.
  • suitable non-ionic promoters include those selected from the group consisting of imidazoles, imidazolines, oxadiazoles, oxazoles, oxazolines, isoxazoles, thiazoles, thiazolines, pyrrolines, pyridines, trihydropyrimidines, pyrazoles, triazoles, isothiazoles, tetrazoles, thiadiazoles, pyridazines, pyrazines, oxazines and dihydrooxazine.
  • Preferred non-ionic promoters include those selected from the group having Formula (I) or Formula (II) as follows: where E is selected from -O-, -S-, -Se-, -CH 2 - and -N(R 8 )-; R 5 is selected from the group consisting of CH 3 and C 2 H 5 (and is preferably CH 3 ); R 6 and R 7 are selected from the group consisting of H, CH 3 , C 6 H 5 (i.e., phenyl), CH 2 C 6 H 5 , CH(CH 3 ) 2 , and fused phenyl; L is selected from the group consisting of -O-, -S-, -Se-, -N(R 8 )-, -C 6 H 4 -, 2,6-pyridyl, -OC 6 H 4 -C 6 H 4 O-, -CH 2 CH 2 OCH 2 CH 2 - and -(CH 2 ) p - where p is an integer from 0
  • each pair of carbon atoms respectively attached to R 6 and R 7 (as represented by the dashed bond lines in Formula (I) and Formula (II) can be either a single or a double bond.
  • compounds of Formula (II) which are optically active are optically active.
  • the effect of the promoter(s) is to enhance the rate and selectivity of the reaction. Frequently, use of the promoter(s) will enable operation of the reaction at a lower temperature, and with an acceptable rate, than would be possible in the absence of the promoter.
  • the process of this invention is carried out in the presence of a solvent.
  • the solvents of this invention divide the reaction mixture into two liquid phases. Suitable solvents for the process of the invention thus include those which not only promote the formation of the 1:1 adduct, but also divide the reaction mixture into two liquid phases.
  • the product addition compound is preferably concentrated in the lower liquid phase, while the solvent and catalyst are preferably concentrated in the top liquid phase.
  • Useful solvents for the process of this invention include certain dinitriles and cyclic carbonate esters. These solvents are commercially available.
  • solvents for the process of this invention include ethylene carbonate, propylene carbonate, butylene carbonate, 1,2-cyclohexane carbonate, malononitrile, succinonitrile, ethyl succinonitrile, glutaronitrile, methyl glutaronitrile, adiponitrile, pimelonitrile, suberonitrile, and mixtures thereof.
  • Preferred solvents for the process of the invention are adiponitrile, glutaronitrile, methyl glutaronitrile, and propylene carbonate.
  • Another important criterion for the choice of solvent is the boiling point of the solvent relative to that of the desired addition compounds. It is preferred that the boiling point of the solvent be higher than the boiling point of the adduct so that easy separation of the adduct from the solvent may be made by distillation.
  • Another important criterion for the choice of solvent is that it serve as a solvent for the catalyst or catalyst/promoter mixture at the reaction temperature or below.
  • the catalyst system comprising the copper(I) compound, the soluble halide promoter, and the solvent, can be prepared in advance in a suitable mixing vessel and then added to the reaction mixture.
  • the individual components of the catalyst system can be added individually to the reactor.
  • the process of the present invention is suitably conducted at a temperature in the range of from about 90°C to 150°C, preferably from about 100°C to about 140°C, and most preferably, from about 110°C to 130°C.
  • the pressure of the process is not critical and can be subatmospheric, atmospheric or superatmospheric, preferably, superatmospheric.
  • the pressure in the system is frequently governed by the vapor pressures of the reactants at the temperature of the reaction.
  • the reaction may be carried out under a pressure of nitrogen or other inert gas diluent.
  • the formation of 2:1 and higher adducts can be further controlled by manipulating reaction variables such as the molar ratio of the halogenated alkane to the alkene.
  • reaction variables such as the molar ratio of the halogenated alkane to the alkene.
  • Higher molar ratios of halogenated alkane to alkene and dilution of the alkene reduce telomer formation. This can be accomplished by continuously feeding the alkene or mixture of the alkene and of the halogenated alkane to a heel of the halogenated alkane and catalyst mixture.
  • the total amount of copper(I) catalyst used in the reaction of this invention is typically at least about 5 mmoles, preferably from about 5 mmole to 700 mmoles, and more preferably from about 10 mmoles to 100 mmoles, per mole of alkene used.
  • the amount of ionic promoter used in the process of this invention is enough to provide about 0.25 to 3.0 mole of halide per gram-atom of copper(I), preferably about 1 mole of halide per gram-atom of copper(I). Use of more or less promoter will not provide the maximum benefit of the promoter.
  • the amount of optional heterocyclic non-ionic promoter used in the reaction of this invention is typically at least an amount sufficient to provide 2 mmol of heterocyclic ring which contains carbon-nitrogen double bonding per mmol of copper catalyst.
  • typically at least about 2 moles of Formula (I) promoter or about 1 mole of Formula (II) promoter is typically used per mole of copper catalyst.
  • the amount of halogenated alkane used in the reaction of this invention is typically at least about 1 mole, and preferably from about 2 moles to 10 moles, per mole of alkene used.
  • the amount of solvent used in the reaction of this invention is typically at least about 5 moles, and preferably from about 10 moles to 100 moles, per mole of copper catalyst used.
  • the process of the present invention facilitates easy separation of the 1:1 addition product of the halogenated alkane to the alkene by taking advantage of the two phase nature of reaction mixture of this invention. That is, the desired 1:1 addition product tends to accumulate in the lower of the two liquid layers while the solvent and the catalyst tend to accumulate in the upper layer.
  • the upper and lower layers may be separated continuously in a separation zone (e.g., a decanter) as is known in the art or on a batch basis by allowing the phases to separate in the reactor or a holding tank and removing the lower layer from the bottom of the vessel.
  • the catalyst and solvent in the upper layer may be re-used for subsequent reactions. Since a small amount of solvent is dissolved in the lower layer and is removed with the product, it is desirable to replace lost solvent in a continuous process.
  • reaction rate is being operated in a continuous manner or if multiple batches are being run with the same catalyst charge, a gradual loss of reaction rate may be observed. A satisfactory reaction rate can be restored by addition of the optional promoter to the reaction.
  • the desired addition product may be separated from any alkene starting material, alkane starting material, solvent, and any higher telomer products by conventional techniques such as distillation.
  • the low boiling fraction will typically be the starting halogenated alkane and the alkene which may be recovered and recycled to the reactor.
  • Higher boiling material will comprise the solvent and any higher boiling telomer by-products.
  • the higher boiling phase may be further refined and the solvent recycled to the reactor.
  • the separation of the two liquid phases in the reactor may be done at temperatures between the reaction temperature and ambient temperature; cooling the reaction mixture lower than room temperature is usually not necessary.
  • reaction zone and its associated feed lines, effluent lines and associated units should be constructed of materials resistant to corrosion.
  • Typical materials of construction include steel reactors lined with poly(tetrafluoroethylene) or glass and glass reactors.
  • addition compounds that comprise the products of this invention are useful as intermediates for the formation of hydrofluoroalkanes. These addition compounds can be reacted with hydrogen fluoride in either the liquid or vapor phase in the presence of a suitable fluorination catalyst.
  • the addition compounds can be reacted with HF in the presence of catalysts selected from the halides of antimony, molybdenum, niobium, tantalum, tin and titanium, and mixtures thereof, preferably, antimony, niobium and tantalum.
  • the temperature of the reaction can be in the range of 50°C to 175°C, preferably, 60°C to 150°C.
  • the pressure is selected so that the reaction medium is maintained in the liquid state, typically between 101 kPa and 5000 kPa, preferably, 1135 kPa to 3203 kPa.
  • 1,1,1,3,3,3-hexachloropropane (HCC-230fa) can be reacted with HF in the liquid phase using halides, fluorosulfonates or triflates of antimony, molybdenum, niobium, tantalum, tin or titanium, or mixtures thereof as catalysts to produce 1,1,1,3,3,3-hexafluoropropane (HFC-236fa).
  • 1-Chloro-1,1,3,3,3-pentafluoropropane (HCFC-235fa) can also be prepared from HCC-230fa.
  • HCFC-235fa can be hydrodechlorinated using a hydrodehalogenation catalyst to produce 1,1,1,3,3-pentafluoropropane (HFC-245fa).
  • a hydrodehalogenation catalyst to produce 1,1,1,3,3-pentafluoropropane (HFC-245fa).
  • Palladium on acid-washed carbon is a preferred catalyst for the conversion of HCFC-235fa to HFC-245fa.
  • carbon tetrachloride can be reacted with vinyl chloride to produce the adduct 1,1,1,3,3-pentachloropropane (i.e., CCl 3 CH 2 CHCl 2 or HCC-240fa).
  • CCl 3 CH 2 CHCl 2 can then be reacted with HF in the liquid phase using the process described above to produce CF 3 CH 2 CHF 2 .
  • the reaction products may be separated by conventional techniques such as distillation. Hydrofluorocarbons such as CF 3 CH 2 CHF 2 form azeotropes with HF; and conventional decantation/distillation may be employed if further purification of the hydrofluorocarbons is desired.
  • the addition compounds can be reacted with HF in the presence of catalysts comprising trivalent chromium.
  • Catalysts prepared by pyrolysis of (NH 4 ) 2 Cr 2 O 7 to produce Cr 2 O 3 and pretreated with HF and catalysts prepared by pretreating Cr 2 O 3 having a surface area greater than about 200 m 2 /g with HF are preferred.
  • the temperature of the reaction can be in the range of 200°C to 400°C, preferably, 250°C to 375°C.
  • the pressure is not critical and is selected so that the reaction starting materials and products are maintained in the vapor state at the operating temperature. For example, it has recently been disclosed in U.S. Patent No.
  • 1,1,1,3,3,3-hexafluoropropane may be prepared in high yield from 1,1,1,3,3,3-hexachloropropane by a vapor phase hydrofluorination process in the presence of a trivalent chromium catalyst.
  • the 2:1 adducts may also be useful intermediates.
  • ADN is CN(CH 2 ) 4
  • HastelloyTM C nickel alloy shaker tube was charged with anhydrous cuprous chloride (1.39 g, 0.014 mole), triethylamine hydrochloride (1.93 g, 0.014 mole), adiponitrile (52.0 g, 0.481 mole), carbon tetrachloride (151.0 g, 0.982 mole), and vinylidene chloride (47.5 g, 0.490 mole).
  • the tube was sealed, cooled in a dry ice bath, evacuated, and purged with nitrogen several times. The tube was placed in a heating jacket and agitation begun.
  • the tube was heated to 120°C over the course of 1.3 hours and then held at 119-122°C for one hour; during this time the pressure rose to a maximum of 83 psig (674 kPa) and then dropped to 41 psig (384 kPa) at the end of the heating period. The tube was then cooled to ambient temperature.
  • the tube was discharged to afford 244.9 g of a product consisting of a dark red brown liquid layer over a pale yellow lower liquid layer.
  • the top layer (109.7 g) was filtered to yield 1.2 of solid.
  • the top and bottom layers were analyzed by gas chromatography and found to have the compositions (in grams) indicated in Table 1 below. Weights of Components, g Component Top Layer Bottom Layer ADN 53.8 2.7 VCl 2 0.1 0.2 CCl 4 23.5 60.0 CCl 3 CH 2 CCl 3 26.8 57.0 CCl 3 (CH 2 CCl 2 ) 2 Cl 3.6 8.4 CCl 3 (CH 2 CCl 2 ) 3 Cl - 0.9
  • Catalyst Promoter CH 2 CCl 2 Conv. %Yield CCl 3 CH 2 CCl 3 C 3 :C 5 Ratio 2 CuCl None 70.3 35.5 10.5 3 CuCl None 72.0 31.6 13.2 4 CuCl 2 None 73.2 30.2 8.4 5 CuCl 2 None 69.8 29.5 9.6 6 CuCl KCl 79.8 44.3 7.7 7 CuCl KBr 71.3 34.8 7.6 8 CuCl KI 87.3 16.1 2.0 9 CuCl KF 67.4 38.5 10.4 10 CuCl [N(C 4 H 9 ) 4 ]Br 89.9 71.4 13.1 1 CuCl [NH(C 2 H 5 ) 3 ]Cl 99.2 68.3 9.7 11 CuCl [N(CH 3 ) 4 ]Br 98.2 58.5 9.0 12 CuCl [N(C 4 H 9 ) 4 ]Cl 99.7 70.3 8.6 13 CuCl [N(C 4 H 9

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Claims (7)

  1. Flüssigphasenverfahren zur Herstellung halogenierter Alkanaddukte der Formel CAR1R2CBR3R4, wobei
    R1, R2, R3 and R4 jeweils unabhängig aus der Gruppe, bestehend aus H, Br, Cl, F, C1-C6-Alkyl, CN, CO2CH3, CH2Cl und Aryl, ausgewählt sind, mit der Maßgabe, daß, wenn entweder R3 oder R4 aus der Gruppe, bestehend aus C3-C6-Alkyl, CN, CO2CH3, CH2Cl und Aryl, ausgewählt ist, dann R1, R2 und das andere von R3 und R4 H sind, und wenn R3 und R4 aus der Gruppe, bestehend aus Cl, F, CH3 und C2H5, ausgewählt sind, dann R1 und R2 H sind, und wenn entweder R1 oder R2 und entweder R3 oder R4 aus der Gruppe, bestehend aus Cl, F, CH3 und C2H5, ausgewählt sind, dann das andere von R1 und R2 und das andere von R3 und R4 H sind;
    A aus der Gruppe, bestehend aus CX3, CH3-aXa, CnH(2n+1)-bXb und CHcX2-cR, ausgewählt ist, wobei R CnH(2n+1)-bXb ist, jedes X unabhängig aus der Gruppe, bestehend aus Br, F, Cl und I, ausgewählt ist, a eine ganze Zahl von 0 bis 3 ist, n eine ganze Zahl von 1 bis 6 ist, b eine ganze Zahl von 1 bis 2n+1 ist und c eine ganze Zahl von 0 bis 1 ist;
    und B aus der Gruppe, bestehend aus Br, Cl und I, ausgewählt ist; mit der Maßgabe, daß (1), wenn A CX3 ist, dann nur eines von X I ist, (2), wenn A CH3-aXa ist, dann jedes X B ist und a 2 ist, wenn B Br oder Cl ist, und a eine ganze Zahl von 0 bis 2 ist, wenn B I ist, und (3), wenn A CnH(2n+1)-bXb ist, dann jedes X unabhängig aus Cl und F ausgewählt ist und B I ist, umfassend:
    Inkontaktbringen eines halogenierten Alkans der Formel AB mit einem Olefin der Formel CR1R2=CR3R4 in Lösungsmittel in Form von Dinitril oder cyclischem Carbonatester, was das Reaktionsgemisch in zwei flüssige Phasen teilt, und in Anwesenheit eines Katalysatorsystems, enthaltend (i) mindestens einen Katalysator, umfassend einwertiges Kupfer; und (ii) mindestens einen ionischen Promotor, ausgewählt aus der Gruppe, bestehend aus substituierten Ammoniumhalogeniden, Pyridinium- und substituierten Pyridiniumhalogeniden sowie quaternären Salzen des Typs (MQ4)Y, wobei M ein Element der Gruppe VA des Periodensystems ist, Q eine C1-C18-Hydrocarbylgruppe ist und Y Cl, Br oder I ist.
  2. Verfahren nach Anspruch 1, wobei AB aus der Gruppe, bestehend aus CCl4, CBrCl3, CCl2FCCl2F, CCl3CClF2, CCl3CF3, CCl3CF2CCl3, CCl3CF2CF3, CCl3CH2CCl3, CCl3CH2CF3, CCl3CF2CClF2, CF3I, CF3CF2I, CF3CFICF3 und CF3CF2CF2I, ausgewählt ist.
  3. Verfahren nach Anspruch 2, wobei das Olefin aus der Gruppe, bestehend aus CH2=CH2, CH2=CHCl, CH2=CHF, CHCl=CHCl, CH2=CCl2, CH2=CF2, CH2=CHCH3, CH2=CHCH2Cl und CH2=CHC6H5, ausgewählt ist.
  4. Verfahren nach Anspruch 1, wenn der Kupferkatalysator aus der Gruppe, bestehend aus Kupfer(I)-Chlorid, Kupfer(I)-bromid, Kupfer(I)-iodid, Kupfer(I)-acetat und Kupfer(I)-thiocyanat, ausgewählt ist.
  5. Verfahren nach Anspruch 1, wobei die Reaktion in einer kontinuierlichen Weise betrieben wird.
  6. Verfahren nach Anspruch 1, wobei das Lösungsmittel aus der Gruppe, bestehend aus Ethylencarbonat, Propylencarbonat, Butylencarbonat, 1,2-Cyclohexancarbonat, Malononitril, Succinonitril, Ethylsuccinonitril, Glutaronitril, Methylglutaronitril, Adiponitril, Pimelonitril, Suberonitril und Gemischen davon, ausgewählt ist.
  7. Verfahren zur Herstellung eines Hydrofluoralkans, umfassend:
    (a) Herstellen eines halogenierten Alkanaddukts der Formel CAR1R2CBR3R4 durch Umsetzen von AB und CR1R2=CR3R4 entsprechend dem Verfahren nach Anspruch 1, mit der Maßgabe, daß R1, R2, R3 und R4 unabhängig aus H, CH3, C2H5, Cl und F ausgewählt sind, B und X Cl sind und mindestens eines von AB und CR1R2=CR3R4 Wasserstoff enthält; und
    (b) Umsetzen des in (a) hergestellten Addukts mit HF.
EP98902505A 1997-01-16 1998-01-07 Verfahren zur herstellung von halogenkohlenwasserstoffen Expired - Lifetime EP0958266B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US3538397P 1997-01-16 1997-01-16
US35383P 1997-01-16
PCT/US1998/000579 WO1998031649A1 (en) 1997-01-16 1998-01-07 Process for the manufacture of halocarbons

Publications (2)

Publication Number Publication Date
EP0958266A1 EP0958266A1 (de) 1999-11-24
EP0958266B1 true EP0958266B1 (de) 2002-04-10

Family

ID=21882347

Family Applications (1)

Application Number Title Priority Date Filing Date
EP98902505A Expired - Lifetime EP0958266B1 (de) 1997-01-16 1998-01-07 Verfahren zur herstellung von halogenkohlenwasserstoffen

Country Status (11)

Country Link
US (1) US6255544B1 (de)
EP (1) EP0958266B1 (de)
JP (1) JP2001508462A (de)
KR (1) KR100509313B1 (de)
CN (1) CN1125012C (de)
BR (1) BR9806750A (de)
CA (1) CA2277169C (de)
DE (1) DE69804770T2 (de)
ES (1) ES2173567T3 (de)
TW (1) TW589294B (de)
WO (1) WO1998031649A1 (de)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6755942B1 (en) 1995-08-01 2004-06-29 E. I. Du Pont De Nemours And Company Process for the manufacture of halocarbons and selected compounds and azeotropes with HF
KR100517576B1 (ko) 1995-08-01 2005-12-21 이.아이,듀우판드네모아앤드캄파니 할로카본의제조방법,선택된화합물및hf함유공비조성물
ES2220547T3 (es) 1999-10-06 2004-12-16 Solvay (Societe Anonyme) Procedimiento de preparacion de hidrocarburos halogenados.
US6547655B1 (en) * 2001-06-29 2003-04-15 Schaffner Manufacturing Company, Inc. Flame-resistant buffing wheel and method
CN109988058B (zh) * 2017-12-29 2021-07-20 山东东岳高分子材料有限公司 一种较短链长全氟烷基碘调聚物的合成方法

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE622939A (de) 1961-09-28
BE1005096A3 (fr) 1991-07-10 1993-04-20 Solvay Procede pour la preparation de 1-chloro-1,1,3,3,3-pentafluoropropane et de 1,1,1,3,3,3-hexafluoropropane.
CN1128016A (zh) 1993-07-29 1996-07-31 联合讯号公司 1，1，1，3，3-五氟丙烷的制备方法
US5414165A (en) 1994-07-29 1995-05-09 E. I. Du Pont De Nemours And Company Process for the manufacture of 1,1,1,3,3,3,-hexafluoropropane
BR9609683A (pt) * 1995-08-01 1999-07-06 Du Pont Processo em fase líquida para produção de adutos de alcano halogenados e processo para produção de um hidrofluoroalcano
KR100517576B1 (ko) * 1995-08-01 2005-12-21 이.아이,듀우판드네모아앤드캄파니 할로카본의제조방법,선택된화합물및hf함유공비조성물

Also Published As

Publication number Publication date
DE69804770D1 (de) 2002-05-16
CN1250430A (zh) 2000-04-12
US6255544B1 (en) 2001-07-03
JP2001508462A (ja) 2001-06-26
TW589294B (en) 2004-06-01
CA2277169C (en) 2007-10-02
BR9806750A (pt) 2000-03-14
ES2173567T3 (es) 2002-10-16
KR100509313B1 (ko) 2005-08-22
KR20000070190A (ko) 2000-11-25
WO1998031649A1 (en) 1998-07-23
EP0958266A1 (de) 1999-11-24
DE69804770T2 (de) 2002-11-21
CA2277169A1 (en) 1998-07-23
CN1125012C (zh) 2003-10-22

Similar Documents

Publication Publication Date Title
US6291730B1 (en) Process for the manufacture of halocarbons and selected compounds and azeotropes with HF
US8884084B2 (en) Process for the manufacture of halocarbons and selected compounds and azeotropes with HF
MXPA98000871A (en) Process for manufacturing halocarburs and selected compounds and azeotropes with
JPH09508138A (ja) １，１，１，３，３−ペンタフルオロプロパンの製造法
US7947856B2 (en) Process for the preparation of halogenated hydrocarbons with at least 3 carbon atoms in the presence of iron and a phosphite
EP0863862B1 (de) Verfahren zur herstellung von halogenkohlenwasserstoffen
EP0958266B1 (de) Verfahren zur herstellung von halogenkohlenwasserstoffen
US6040487A (en) Process for the manufacture of halocarbons
US6452057B1 (en) Process for preparing halohydrocarbons in the presence of a co-catalyst
MXPA99006456A (en) Process for the manufacture of halocarbons
EP1908745A1 (de) Verfahren zur Herstellung von halogenierten Kohlenwasserstoffen mit mitdestens 3 Kohlenatomen aus CFCl3 und einer Olefine

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 19990623

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): DE ES FR GB IT NL

17Q First examination report despatched

Effective date: 20001016

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

REG Reference to a national code

Ref country code: GB

Ref legal event code: IF02

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): DE ES FR GB IT NL

REF Corresponds to:

Ref document number: 69804770

Country of ref document: DE

Date of ref document: 20020516

ET Fr: translation filed
REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2173567

Country of ref document: ES

Kind code of ref document: T3

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 20030130

Year of fee payment: 6

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed

Effective date: 20030113

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20040108

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20040108

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20110128

Year of fee payment: 14

Ref country code: IT

Payment date: 20110115

Year of fee payment: 14

Ref country code: NL

Payment date: 20110117

Year of fee payment: 14

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20110105

Year of fee payment: 14

REG Reference to a national code

Ref country code: NL

Ref legal event code: V1

Effective date: 20120801

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20120107

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20120928

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20120107

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20120107

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20120131

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20120801

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20130103

Year of fee payment: 16

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 69804770

Country of ref document: DE

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 69804770

Country of ref document: DE

Effective date: 20140801

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20140801